CHM 302 - Inorganic Chemistry III – 3 Units

LECTURE 4
Dr Thompson Izuagie

Chemistry of Boron

13
B
5
 PRE-LECTURE QUESTIONS

 Which of the Group 13 elements is the most abundant?

 Which group of the Periodic Table is the difference between the first

member and its congeners more prominent?

 What compounds are used in making Pyrex glass and why?

 What do you understand by the term ‘Cluster’?

 What do you understand by the term ‘Zintl’?

 Review of Lecture 3
 Properties of Group 2 elements
 Atypical (Anomalous) properties of Beryllium
 Occurrence and extraction
 Simple compounds
• Hydrides
• Halides
• Hydroxides
• Oxides and Related compounds
• Sulfides, nitrides and carbides
• Compounds of oxoacids
 Coordination compounds of Group 2 elements
 Organometallic compounds of Group 2 elements
 Uses of Group 2 elements and their compounds
 Outline
 Properties of boron
 Anomalous behaviour of boron
 Occurrence and extraction of boron
 Compounds of boron
• Hydrides
 Lewis acidity
 Hydroboration
• Halides
• Boron-oxygen compounds
• Boron-nitrogen compounds
• Metal borides
• Boron clusters
 Borohydrides
 Metallaboranes
 Carboranes
 Organometallic compounds
 Uses of boron and its compounds
 Objectives
• To understand the occurrence and extraction of boron
• To become more familiar with the reactions of boron and
its compounds
• To understand the properties of boron

• To become more familiar with the applications of boron

and their compounds
 Group 13 Elements

Boron Aluminum Gallium Indium Thallium Nihonium

13
5
B
13
Al

31
Ga
49
In
81
Th

113
Nh

 The common difference between the first member of a Group and its
congeners in the Periodic Table is mostly evident in Group 13 where the
chemical properties of B are very distinct from those of the rest of the group.
 Boron is as a result the only nonmetal in Group 13.
 Properties
 The valence electron configuration of the Group 13 elements is ns2np1 and,
as this configuration suggests, all the elements adopt the +3 oxidation state
in their compounds.
 The electron configuration of boron is thus [He] 2s22p1
 Boron exists in several allotropes. Amorphous B is a brown powder but the
hard and refractory crystalline B forms shiny black crystals.

Amorphous B Crystalline B
 The three solid phases for which crystal structures
are available contain the icosahedral (20-faced) B12
unit as a building block. B12 icosahedron in
elemental boron
 Boron is inert, and under normal conditions finely
divided B is attacked only by F2 and HNO3.
 Anomalous behaviour of boron
 Boron, the first member of the group differs from its congeners on account
of its small atomic radius.
 This difference is mostly evident in Group 13 where the chemical properties
of B are distinct from those of the rest of the group.
 However, B does have a pronounced diagonal relationship with Si in Group
14.
• Boron and silicon form acidic oxides, B2O3 and SiO2
• Boron and Silicon form many polymeric oxide structures and glasses
• Boron and silicon form flammable, gaseous hydrides.

Occurrence and Extraction

 Boron occurs naturally as borax, Na2B4O5(OH)4.8H2O, and kernite,
Na2B4O5(OH)4.2H2O, from which the impure element is obtained.
 The borax is converted to boric acid, B(OH)3, and then to boron oxide, B2O3.
The oxide is reduced with magnesium and washed with alkali and then
hydrofluoric acid.
 Pure B is produced by reduction of BBr3 vapour with H2:
2BBr3(g) + 3H2(g) → 2 B(s) + 6 HBr(g)
 Compounds of boron

Hydrides Halides Boron-oxygen Boron-nitrogen Metal borides

compounds compounds
 A very important feature of boron (and the lighter Group 13 elements) is
their ns2np1 electron configuration, which contributes up to a maximum of
six electrons in the valence shell when three covalent bonds are formed
by electron sharing. As a result, many of their compounds have an
incomplete octet and act as Lewis acids, being able to complete their
octet by accepting a pair of electrons from a donor.
Hydrides
 The binary hydrogen compounds of B are called boranes.
The simplest member of the series is diborane, B2H6.
 It is electron-deficient and its structure is commonly described in terms of
two-centre two-electron (2c, 2e) and three-centre two-electron (3c,
2e) bonds: bridging 3c, 2e bonds are a recurring theme in borane
 Diborane,
chemistry. B2H6, can be prepared in the laboratory by metathesis of a boron
halide with either LiAlH4 or LiBH4 in ether:
3 LiBH4(ether) + 4BF3(ether) → LiBF4(ether) + 2 B2H6 (g)
 Diborane is a Lewis acid and it decomposes slowly at room temperature.
 Higher boranes exist and can be liquids such as B5H9 and solids such as
B10H14. They can be prepared by partial pyrolysis of diborane
 All the boron hydrides are flammable, sometimes explosively and many of
them are susceptible to hydrolysis.
 All the boranes are colourless and diamagnetic.
 Alkali metal tetrahydridoboranates, NaBH4 and LiBH4, are very useful in
the laboratory as general reducing agents and as precursors for most-
boron-hydrogen compounds. Alkali and alkali earth metal
tetrahydridoboranes and ammonia borane, NH 3BH3, are useful hydrogen
storage materials.
Lewis acidity
 Diborane and many light boron hydrides act
as Lewis acids and are cleaved by reaction
with Lewis bases. Two different cleavage 2L 2L
patterns have been observed, namely
symmetrical cleavage and unsymmetrical.
 Soft and bulky Lewis bases cleave diborane,
B2H6 symmetrically into two BH3 fragments.
 More compact and hard Lewis bases cleave
the hydrogen bridge unsymmetrically.
 Although it reacts with many hard Lewis bases, diborane is best regarded
as a soft Lewis acid.
Hydroboration
 Hydroboration, the reaction of diborane with alkenes in ether solvent,
produces organoboranes that are useful intermediates in synthetic organic
chemistry. ∆/ether
H3B–OR2 + H2C=CH2 CH3CH2BH2 + R2O
The tetrahydridoborate ion
 Diborane reacts with alkali metal hydrides to produce salts containing the
tetrahydridoborate ion, BH4–.
 The tetrahydridoborate ion is a useful intermediate for the preparation of
metal hydride complexes and borane adducts.
Halides
 Boron trihalides consist of trigonal-planar BX3 molecules.
 Boron trifluoride and boron trichloride are gases, the tribromide
is a volatile liquid, and the triiodide is a solid. This trend in
volatility is consistent with the increase in strength of dispersion
forces with the number of electrons in the molecules.
 All the boron trihaldies except BI3 may be prepared by direct reaction
between the elements. However, the preferred method for BF 3 is the
reaction of B2O3 with CaF2 in H2SO4.
 Boron trihalides have an incomplete octet and are Lewis acids. The order of
Lewis acidity is BF3 < BCl3 ≤BBr3. The trend in Lewis acidity stems from
more efficient X—B π bonding for the lighter, smaller halogens, the F—B
bond being one of the strongest formally single bonds known.
 All the boron trihalides form simple Lewis complexes with suitable bases
as in the reaction: BF3(g) + :NH3(g) → F3B–NH3(s)
 Boron chlorides, bromides, and iodides are susceptible to protolysis by
mild proton sources such as water, alcohols, and even amines.
BCl3(g) + 3 H2O(l) → B(OH)3(aq) + 3 HCl(aq)
 Boron halides containing B–B bonds have been prepared. The best known
of these compounds have the formula B2X4, with X = F, Cl, or Br and the
tetrahedral cluster compound B4Cl4.
 Boron-oxygen compounds
 Boric acid, B(OH)3, is a very weak Bronsted acid in aqueous solution.
 The reaction of boric acid with an alcohol in the presence of sulfuric acid
produces simple borate esters with the formula, B(OR)3:
H2SO4
B(OH)3 + 3 CH3OH B(OCH3)3 + 3 H2O
 The borate esters are weaker Lewis acids than the trihalides.
 The most important oxide of B, B2O3, is prepared by dehydration of boric
acid.
4 B(OH)3(s) → 2 B2O3(s) + 6 H2O(l)
 Crystalline B2O3 consists of an ordered network of BO3 linked by O atoms.
The vitreous form consists of an array of partially ordered trigonal BO 3 units.
 The rapid cooling of molten B2O3 or metal borates often leads to the
formation of borate glasses. Though it has low technological use.
 Sodium borate is fused with silica to form borosilicate glasses (such as
Pyrex®). Borosilicate glasses are resistant to thermal shock and can be
heated over a flame due to the strong B—O bonds. Thus, are used to
make heat-resistant laboratory glassware.
 Many polynuclear borates (both cyclic and chain species) are known. An
example is the cyclic polyborate anion, B3O63–.
 Boron-nitrogen compounds
 Many molecular compounds exist that are similar to carbon compounds
that possess BN bonds. The similarities between compounds containing
BN and CC units can be explained by the fact that these units are
isoelectronic. The simplest compound of B and N, boron nitride, BN, is
easily synthesized by heating boron oxide with a nitrogen compound:
B2O3(l) + 2 NH3(g) → 2 BN(s) + 3 H2O (g)
 The structure of one form of boron nitride consists of planar sheets of
atoms like those in graphite, and some of the physical properties of BN are
similar to those of graphite. For example, both graphite and BN have a
slippery feel and are used as lubricants. However, BN is a white,
nonconducting solid, not a black, metallic conductor.
 Apart from layered boron nitride, the best-know unsaturated compound of
B and N is borazine, B3N3H6, which is isoelectronic and isostructural with
benzene and, like benzene, is a colourless liquid (b.p. 55 oC).

Benzene Borazine
 Another example of BN compound is the ethane analogue ammonia
borane, H3NBH3 (an ammine-borane).
Metal borides
 The direct reaction of elemental boron and a metal at high temperatures
provides a useful route to many metal borides. An example is the reaction
of Ca and some other highly electropositive metals with B to produce a
phase of composition MB6: Ca(l) + 6 B(s) → CaB6(s)
Boron clusters
 Boron forms an extensive range of polymeric, cage-like clusters which
include the borohydrides, metallaboranes, and carboranes.

Boron clusters

Borohydrides Metallaboranes Carboranes

Borohydrides
 In addition to the simple hydrides, B forms several series of neutral and
anionic polymeric cage-like boron-hydrogen compounds. Borohydrides are
formed with up to 12 B atoms and fall into three classes called closo, nido
and arachno.
 The borohydrides with the formula [BnHn]2– have a closo structure, a name
derived from the Greek for ‘cage’. This series of anions is known for n = 5
to 12, and examples include the trigonal-bipyramidal [B5H5]2– ion, the
octahedral [B6H6]2– and the icosahedral [B12H12]2– ion. When boron clusters
have the formula BnHn+4 they adopt the nido structure, a name derived
from the Latin for ‘nest’. An example is B5H9. Clusters of the formula
[BnHn+6] have an arachno structure, from the Greek for ‘spider’ (as they
resemble untidy siders’ webs). One example is pentaborane (B5H11).
Metalloboranes
 Boron forms many metal-containing clusters, called the metallaboranes.
In some cases the metal is attached to a borohydride ion through hydrogen
bridges, i.e. B-H-M. A more common and generally more robust group of
metallaboranes have direct M—B bonds.
Carboranes
 Closely related to the polyhedral boranes and borohydrides are the
carboranes (more formally, the carbaboranes), a large family of clusters
that contain both B and C atoms. An analogue of B6H62– is the neutral
carborane B4C2H6. Other heteroatoms such as N, P, and As can also be
introduced into boranes.
Organometallic Compounds
 Organoboron compounds are commonly treated as organometallic
compounds even though B is not a metal.
 Organoboron compounds are electron-deficient and act as Lewis acids;
tetraphenylborate is an important ion.

Uses of boron and its compounds

 The main use of B is in borosilicate glasses.
 Borax has many domestic uses for example as a water softener, cleaner
and mild pesticide.
 Boric acid, B(OH)3, is used as a mild antiseptic.
 Amorphous brown boron is used in pyrotechnics to impart a bright green
colour.
 Lightweight, strong boron filaments are used in composite materials for the
aerospace industry and in sports equipment.
 Many compounds of B are superhard materials, having hardness
approaching that of diamond.
 The material known as ‘heterodiamond’, sometimes labelled BCN, is
formed from diamond and boron nitride by explosive shock synthesis.
These compounds are used as substitutes for diamond in cutting tools
and blades.
 Uses of boron and its compounds

 Sodium perborate, NaBO3.H2O, which exists as the dimer Na2B2O4(OH)4,

is used as a chlorine-free bleach in laundry products, cleaning
materials, and tooth whitener. It is less aggressive to textiles than chlorine
bleaches and active at low temperature when mixed with an activator such
as tetraacetylethylenediamine (TAED).

 Sodium hydridoborate, NaBH4, is used on a massive scale for bleaching

wood pulp.
 Boranes used to be popular as rocket fuels but were found to be too
pyrophoric to be handled safely. Boranes are being investigated as
possible hydrogen storage materials, with the hydrogen stored as the
ammonia-borane complex NH3:BH3.